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Anthonysamy, A.,Lee, Y.,Karunagaran, B.,Ganapathy, V.,Rhee, S.-W.,Karthikeyan, S.,Kim, K. S.,Ko, M. J.,Park, N.-G.,Ju, M.-J.,Kim, J. K. Royal Society of Chemistry 2011 Journal of materials chemistry Vol.21 No.33
<P>We synthesized hydrophobic ruthenium(<SMALL>II</SMALL>) sensitizers (SY-04 and SY-05) with high molar extinction coefficient by extending the π-conjugation of 3,4- or 3-alkylthiophene-substituted bipyridine ligands. Both dyes displayed a remarkably high molar extinction coefficient of 21.7 × 10<SUP>3</SUP> M<SUP>−1</SUP> cm<SUP>−1</SUP> arising from red-shift of their metal-to-ligand charge transfer band when compared to a commonly used N3 sensitizer. The solar-to-electrical energy conversion efficiency (<I>η</I>) of the SY-04 based dye-sensitized solar cell (DSC) was 7.70%, which is 27% higher than that (6.05%) of the N3-based DSC under the same cell fabrication conditions. The increased <I>η</I> was attributed to the increase in life time and recombination half-life measured by electrochemical impedance and transition absorption spectroscopy, respectively. Density functional theory and time-dependent density functional theory calculations of two dyes in both gas phase and solution were performed. The calculated values of the highest occupied and the lowest unoccupied molecular orbitals and absorption spectra are in good agreement with the experimental results.</P> <P>Graphic Abstract</P><P>DSCs based on hydrophobic ruthenium(<SMALL>II</SMALL>) sensitizers with thiophene-substituted bipyridine ligands showed the solar-to-electrical energy conversion of 7.70%, which is 27% higher than that of N3-based DSC at the same fabrication condition. <IMG SRC='http://pubs.rsc.org/services/images/RSCpubs.ePlatform.Service.FreeContent.ImageService.svc/ImageService/image/GA?id=c1jm11760b'> </P>
Low temperature adsorption of nitric oxide on cerium impregnated biomass-derived biochar
Shahreen Izwan Anthonysamy,Pooya Lahijani,Maedeh Mohammadi,Abdul Rahman Mohamed 한국화학공학회 2020 Korean Journal of Chemical Engineering Vol.37 No.1
This study investigates the catalytic oxidation of NO to NO2 over biomass-derived biochar at ambient temperature. Rubber seed shell (RSS) was used as lignocellulosic waste to develop biochar for NO capture. The NO adsorption capacity of pristine biochar was low, about 17.61mg/g at 30 oC. To enhance the NO uptake capacity of biochar, cerium (Ce) was introduced into the biochar surface through simple impregnation method. Upon this, the NO adsorption capacity of 3 wt% Ce-loaded biochar profoundly increased to 75.59mg/g at the same adsorption condition. This was confidently due to the excellent oxygen storage capacity of ceria which could react with free active sites on the biochar surface to form oxidized cites C(O). Characterization results indicated that the adsorbed species was in the form of -O-N=O, suggesting that the adsorption of NO was followed by reaction with surface oxidized sites to form NO2. Studying the kinetics of the NO adsorption using pseudo-second order, Avrami and Elovich models showed that chemisorption was the chief mechanism that governed the adsorption process and the activation energy for NO adsorption was estimated to be around 45 kJ/mol.
Jeong, Inyoung,Jo, Changshin,Anthonysamy, Arockiam,Kim, Jung-Min,Kang, Eunae,Hwang, Jongkook,Ramasamy, Easwaramoorthi,Rhee, Shi-Woo,Kim, Jin Kon,Ha, Kyoung-Su,Jun, Ki-Won,Lee, Jinwoo Wiley-VCH 2013 ChemSusChem Vol.6 No.2
<P>A disulfide/thiolate (T(2)/T(-)) redox-couple electrolyte, which is a promising iodine-free electrolyte owing to its transparent and noncorrosive properties, requires alternative counter-electrode materials because conventional Pt shows poor catalytic activity in such an electrolyte. Herein, ordered mesoporous tungsten suboxide (m-WO(3-x)), synthesized by using KIT-6 silica as a hard template followed by a partial reduction, is used as a catalyst for a counter electrode in T(2)/T(-)-electrolyte-based dye-sensitized solar cells (DSCs). The mesoporous tungsten suboxide, which possesses interconnected pores of 4 and 20 nm, provides a large surface area and efficient electrolyte penetration into the m-WO(3-x) pores. In addition to the advantages conferred by the mesoporous structure, partial reduction of tungsten oxide creates oxygen vacancies that can function as active catalytic sites, which causes a high electrical conductivity because of intervalence charge transfer between the W(5+) and W(6+) ions. m-WO(3-x) shows a superior photovoltaic performance (79 % improvement in the power conversion efficiency) over Pt in the T(2)/T(-) electrolyte. The superior catalytic activity of m-WO(3-x) is investigated by using cyclic voltammetry (CV), electrochemical impedance spectroscopy (EIS), and Tafel polarization curve analysis.</P>
Moon, Hong Chul,Anthonysamy, Arockiam,Kim, Jin Kon American Chemical Society 2011 Macromolecules Vol.44 No.7
<P>We have demonstrated a facile synthetic route for well-defined poly(3-hexylthiophene)-<I>block</I>-poly(methyl methacrylate) copolymer (P3HT-<I>b</I>-PMMA) by anionic coupling reaction. For successful coupling reaction, newly generated anions should be more stable (less reactive) than initial anions of reactants. In this study, we chose α-phenyl acrylate (PA)-capped P3HTs for successful coupling with living PMMA anions because the anions at PA group are more stable than living PMMA anions. We found that all of the PA groups located at the end of P3HT were completely coupled with living PMMA anions having slightly excess amount (1.5 equiv relative to PA-capped P3HT). The unreactive PMMA homopolymers in crude product were completely removed by using column chromatography, resulting in narrow molecular weight distribution of pure P3HT-<I>b</I>-PMMA. The optical property and thin film morphology of the P3HT-<I>b</I>-PMMA were investigated by using UV−vis spectra and atomic force microscopy, respectively.</P><P><B>Graphic Abstract</B> <IMG SRC='http://pubs.acs.org/appl/literatum/publisher/achs/journals/content/mamobx/2011/mamobx.2011.44.issue-7/ma200171m/production/images/medium/ma-2011-00171m_0004.gif'></P>
Ramasamy, Easwaramoorthi,Jo, Changshin,Anthonysamy, Arockiam,Jeong, Inyoung,Kim, Jin Kon,Lee, Jinwoo American Chemical Society 2012 Chemistry of materials Vol.24 No.9
<P>Ordered mesoporous titanium nitride-carbon (denoted as OM TiN-C) nanocomposite with high surface area (389 m<SUP>2</SUP> g<SUP>–1</SUP>) and uniform hexagonal mesopores (ca. 5.5 nm) was facilely synthesized via the soft-template method. As a structure-directing agent, Pluronic F127 triblock copolymer formed an ordered structure with inorganic precursors, resol polymer, and prehydrolyzed TiCl<SUB>4</SUB>, followed by a successive heating at 700 °C under nitrogen and ammonia flow. In this study, the amorphous carbon within the parent OM TiO<SUB>2</SUB>-C acted as a rigid support, preventing structural collapse during the conversion process of TiO<SUB>2</SUB> nanocrystals to TiN nanocrystals. The OM TiN-C was then successfully applied as counter electrode material in dye-sensitized solar cells (DSCs). The organic electrolyte disulfide/thiolate (T<SUB>2</SUB>/T<SUP>–</SUP>) was introduced to study the electrocatalytic property of the OM TiN-C nanocomposite. Because of the existence of TiN nanocrystals and the defect sites of the amorphous carbon, the DSCs using OM TiN-C as a counter electrode showed 6.71% energy conversion efficiency (platinum counter electrode DSCs: 3.32%) in the organic electrolyte system (T<SUB>2</SUB>/T<SUP>–</SUP>). Furthermore, the OM TiN-C counter electrode based DSCs showed an energy conversion efficiency of 8.41%, whereas the DSCs using platinum as a counter electrode showed a conversion efficiency of only 8.0% in an iodide electrolyte system. The superior performance of OM TiN-C counter electrode resulted from the low charge transfer resistance, enhanced electrical conductivity, and abundance of active sites of the OM TiN-C nanocomposite. Moreover, OM TiN-C counter electrode showed better chemical stability in organic electrolyte compared with the platinum counter electrode.</P><P>Ordered mesoporous titanium nitride-carbon (OM TiN-C) nanocomposites were synthesized, for the first time, using a simple soft-template method. The iodine-free organic electrolyte dye-sensitized solar cells using OM TiN-C nanocomposite counter electrodes exhibited high efficiency (6.71%), that is, a performance 2-fold greater than that of conventional Pt counter electrode DSCs (fill factor: 0.33, efficiency: 3.32%).</P><P><B>Graphic Abstract</B> <IMG SRC='http://pubs.acs.org/appl/literatum/publisher/achs/journals/content/cmatex/2012/cmatex.2012.24.issue-9/cm203672g/production/images/medium/cm-2011-03672g_0012.gif'></P><P><A href='http://pubs.acs.org/doi/suppl/10.1021/cm203672g'>ACS Electronic Supporting Info</A></P>